Substituted phenylethyl sulfites useful for controlling mites

ABSTRACT

This invention relates to compounds of the formulas:   WHERE R&#39;&#39; is aromatic and R and R&#39;&#39;&#39;&#39;are aromatic or aliphatic, which are useful for controlling mites.

United States Patent [191 Covey et a1.

1 1 SUBSTITUTED PHENYLETHYL SULFITES USEFUL FOR CONTROLLING M-lTES' [75]Inventors: Rupert A. Covey, Wolcott; Allen E.

Smith, Bethany; Winchester L. Hubbard, Woodbridge, all of Conn.

[73] Assignee: Uniroyal, Inc., New York, NY.

[22] Filed: June 28, 1973 [21] App]. No.: 374,297

Related US. Application Data [62] Division of Ser. No. 685,226, Nov.- 1,1967, Pat. No.

Hoeffelman 260/456 Jan. 21, 1975 Harris 260/456 X 2,620,359 12/1952Britton et a1... 260/611 A 3,179,682 4/1965 Covey et a1 260/4563,401,120 9/1968 Chiddix et a1. 260/611 A X 3,463,859 8/1969 Covey eta1. 260/456 X Primary ExaminerStanley l Friedman AssistantExaminer'A11en .1. Robinson Attorney, Agent, or Fir'mWillard R. Sprowls,Esq.

[ 7] ABSTRACT This'invention relates to compounds of the formulas:-

where R is aromatic and R and R"are aromatic or aliphatic, whichareuseful for controlling mites.

2 Claims, No Drawings SUBSTITUTED PHENYLETHYL SULFITES USEFUL FORCONTROLLING MITES This is a division of application Ser. No. 685,226,filed Nov. l, 1967, now U.S. Pat. No. 3,775,958 issued Nov. 27, 1973.

This invention relates to new compositions of matter, specifically,mixed sulfite diesters of aliphatic or aromatic alcohols and anaryl-substituted ethylene glycol ether.

The compounds of the invention are useful for controlling mites.

The compounds of this invention may be represented by either of the twogeneral formulas:

O R GIICHaO 8 OR and ROCHafiHIO g OR where R has up to 15 carbon atomsand is aryl, alkaryl, alkoxyaryl or haloaryl, R is alkyl having up to 18carbon atoms or, aryl, alkaryl, haloaryl having up to l carbon atoms, R"is aliphatic, e.g., alkyl having up to 18 carbon atoms, alkenyl havingfrom 3 to carbon atoms, alkynyl having 3 to 10 carbon atoms or,cycloalkyl, haloalkyl, cyanoalkyl and alkoxyalkyl having up to 18 carbonatoms or aromatic, e.g., aryl, haloaryl, alkoxyaryl, alkaryl andcycloalkaryl having up to carbon atoms.

Examples of R are phenyl, l-naphthyl, 2-naphthyl, p-tolyl, o-tolyl,2-methyl-4-t-butylphenyl, isopropylphenyl, tert.-butylphenyl,tert.-amylphenyl, nonylphenyl, cyclohexylphenyl, methoxyphenyl,bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl,pentachlorophenyl.

Examples of R are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,see-butyl, tert.-butyl, amyl, hexyl, 2- ethylhexyl, octyl, decyl,isodecyl, dodecyl, hexadecyl, octadecyl, phenyl, l-naphthyl, 2-naphthyl,p-tolyl, otolyl, 2-methyl-4-t-butylphenyl, isopropylphenyl, tert.-butylphenyl, tert.-amylphenyl, nonylphenyl, bromophenyl, 2-chlorophenyl,2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl.

Examples of R" are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec.-butyl, tert.-butyl, amyl, hexyl, 2- ethylhexyl, octyl, decyl,isodecyl, dodecyl, hexadecyl, octadecyl, allyl, methallyl, alkynylradicals having 3 to 10 carbon atoms, e.g., propargyl and l-(3-nonynyl),

cyclohexyl, 4-methoxycyclohexyl, 2-chloroethyl, 2,2,2,-trichloroethyl,'y-chloropropyl, 2,4- dichlorobutyl, w-trichloroamyl, 2-cyanoethyl, me-

thoxyethyl, sec.-butoxyisopropyl, phenyl, l-naphthyl, 2-naphthyl,p-tolyl, o-tolyl, 2-methyl-4-t-butylphenyl, isopropylphenyl,tert.-butylphenyl, tert.-amylphenyl, nonylphenyl, cyclohexylphenyl,chloromethylphenyl, methoxyphenyl, bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl.

Examples of sulfite diesters of the present invention are:

methyl l-phenyl-2-methoxyethyl sulfite ethyl 2-phenyl-2-methoxyethylsulfite butyl 2-phenyl-2-ethoxyethyl sulfite methyll-phenyl-2-butoxyethyl sulfite methyl l-phenyl-2-decoxyethyl sulfiteoctyl 2-phenyl-2-phenoxyethyl sulfite allyl l-phenyl-Z-o-toloxyethylsulfite propargyl 2-phenyl-2-p-toloxyethyl sulfite 2 l-( 2-butynyl)l-phenyl-2-p-isopropylphenoxyethyl sulfite cyclohexyl1-phenyl-2-p-t-butylphenoxyethyl sulfite 2-chloroethyl2-phenyl-2-p-t-butylphenoxyethyl sulfite Z-cyanoethyll-phenyl-Z-m-toloxyethyl sulfite methoxyethyll-p-tolyl-2-o-chlorophenoxyethyl sulfite phenylZ-m-methoxyphenyl-2-p-chlorophenoxyethyl sulfite o-tolyll-phenyl-2-o-t-butylphenoxyethyl sulfite p-t-butylphenyl2-o-chlorophenyl-2-p-tbutylphenoxyethyl sulfite o-chlorophenyll-phenyl-2-p-toloxyethyl sulfite m-tolyll-m-tolyl-2-p-t-butylphenoxyethyl sulfite methoxyphenyl2-phenyl-2-o-chlorophenoxyethyl sulfite The compounds of this inventionmay be prepared by reacting an alcohol or phenol with the separatelyprepared chlorosulfinate of a selected glycol monoether, which may bemade by reacting the glycol ether with thionyl chloride. The glycolether may be made by reacting an alcohol or phenol with styrene oxide ora substituted styrene oxide. A mixture of two isomeric glycol ethersgenerally is formed, one of which is a primary and the other a secondaryalcohol, and the amount of each depends on the direction of opening ofthe oxide ring. The ratio of the isomers can beyaried depending on thecatalyst used. Such preparations are illustrated by the followingreactions with the same symbols R, R and R as in the above generalformulas.

ROII Gin-(Int Roomuuoll ROICHCIIQOII R R R noun-2011011 soonkoullgcnoiim It R l ()(llll(lll 0ll SOCI: Rocncmosol ROUllCllgOS R.

Alternatively some of the compounds of this invention may be prepared byreacting the glycol ether with the chlorosulfinate of an alcohol asillustrated in the following reaction 0 lwomollolt ClSUClIgClIzCl ll R0CH:(|JHO S O CHeCliaCl The chemicals of the present invention may beapplied to various manners for the control of insects. They may beapplied to loci to be protected against insects as dusts when admixedwith or absorbed on powdered solid carriers, such as the various mineralsilicates, e.g. mica, talc, pyrophyllite and clays, or as liquids orsprays when in a liquid carrier, as in solution in a suitable solvent,such as acetone, benzene or kerosene, or dispersed in a suitablenon-solvent medium, for example, water. In protecting plants (the termincluding plant parts) which are subject to attack by insects, thechemicals of the present invention are preferably applied as aqueousemulsions containing a surface- ;ictive dispersing agent, which may bean anionic, nonionic or cationic surface-active agent. Suchsurfaceactive agents are well known and reference is made to US. Pat.No. 2,547,724, columns 3 and 4 for detailed examples of the same. Thechemicals of the invention may be mixed with such surface-activedispersing agents, with or without an organic solvent as insecticidalconcentrates for subsequent addition of water to make aqueoussuspensions of the chemicals of the desired concentration. The chemicalsof the invention may be admixed with powdered solid carriers, such asmineral silicates together with a surface-active dispersing agent sothat a wettable powder may be obtained, which may be applied directly toloci to be protected against insects, or which may be shaken up withwater to form a suspension of the chemical (and powdered solid carrier)in water for application in that form. The chemicals of the presentinvention may be applied to loci to be protected against insects by theaerosol method. Solutions for the aerosol treatment may be prepared bydissolving the chemical directly in the aerosol carrier which is liquidunder pressure but which is a gas at ordinary temperature (e.g., 20C.)and atmospheric pressure, or the aerosol solution may be prepared byfirst dissolving the chemical in a less volatile solvent and thenadmixing such solution with the highly volatile liquid aerosol carrier.The chemicals may be used admixed with carriers that are active ofthemselves, for example, other insecticides, fungicides or bactericides.

The amount of chemical which is used for control of mites varies widelydepending largely on the amount of foliage to be covered. From as littleas 1 oz. per acre on a young field crop to six pounds or more per acreon an orchard may be used. This could be applied in, as little as 5gallons of liquid by airplane spray application, or in as much as 600gallons with a more conventional ground sprayer which drenches thefoliage.

Dust applications, similarly, would vary in the amounts of materialrequired to control mites as do the liquid spray preparation with therange of active ingredient needed per acre comparable to that used inthe spray applications.

Aerosol treatments of confined areas such as a greenhouse would rangefrom l/2 oz. to 8 oz. of active material for 10,000 cu. ft. of space tobe treated.

The preparation of the gylcol ether can be illustrated by the followingexample EXAMPLE I l-(or 2-) Phenyl-2-p-t-butylphenoxyethanolp-Tert.-butylphenol (112 g., 0.75 mole) and 2.2 g.

sodium hydroxide were combined and themixture heated to 150. Styreneoxide (85.5 ml., 90.0 g., 0.75

mole) was added during three hours maintaining the reaction temperatureat l50-l60. The mixture was cooled, the catalyst was neutralized withconcentrated hydrochloric acid, and the product taken up in xylene. Thexylene was distilled off leaving the crude product which is a mixture of1- and 2-phenyl p-tbutylphenoxyethanol. The mixture can be used directlyin making the sulfite esters or can be distilled, b.p. 140l47 (0.1 mm.).Upon standing, crystals formed in the distillate which, afterrecrystallization from hexane, melted 9698.

The chlorosulfinates can be prepared by well-known reactions (see US.Pat. No. 3,179,682 to 687 and 2,529,494 for examples of theirpreparations).

The preparation of the sulfite esters is carried out in the presence ofan HCl acceptor, such as pyridine, dimethylaniline 0r trimethylamine,and in a solvent such as benzene, xylene or solvent naphtha. Thereaction temperature is generally between -l0 and 50, preferably near 0.

The following example illustrates the preparation of the sulfite esters.

EXAMPLE II B-Chloroethyl l-(or 2-) Phenyl-Z-p-tbutylphenoxyethyl Sulfitel-(or 2-) Phenyl-Z-p-t-butylphenoxyethanol (7.0 g., 0.026 mole), 2.3 ml.(2.2 g., 0.029 mole) pyridine and 50 ml. xylene were combined and thesolution was cooled to 0-5. A solution of 4.7 g. (0.029 mole),B-chloroethyl chlorosulfinate in 20 ml. xylene was added during 15min., keeping the temperature below 15. The mixture was stirred for 30min. and then washed successively with two 25 ml. portions water, 25 ml.2N NaOH and several portions of saturated salt solution until the lastportion was neutral to pH paper. The xylene was removed under reducedpressure and the residue heated to 100 (0.7 mm.) to remove volatileimpurities. The residue was slurried with Dicalite (filteraid) andfiltered, giving 8.6 g. (83.5%) of viscous liquid. Anal. Calcd. for C HClO S: S, 8.08. Found: 7.94, 7.98.

Sulfur analyses'of other chemicals of the present invention were:

Propargyl l-(or 2-)phenyl-2-p-t-butylphenoxyethyl sulfite. Calculated S:8.67. Found: 7.79, 7.64.

o-Tolyl l-(or 2-)phenyl-2-p-t-butylphenoxyethyl sulfite. Calculated S:7.55. Found: 6.79, 7.09.

Infrared spectra obtained on all of the prepared sulfites of thisinvention showed sulfite absorption at 8.3 and were consistent with thestructures. To show that the compounds of the present invention areeffective for controlling mites the following Example is set forth:

EXAMPLE III Pinto beans in the two-leaf stage and grown in 4" basketsunder greenhouse conditions at -75F. were used. Three plants for a totalof six leaves were in each basket for each test. The tests on thechemicals and checks were replicated once. Aqueous suspensions of thechemicals were prepared by adding to 0.2 gram of the chemical one drop(0.03 gram) of a commercial surface-active dispersing agent(isooctylphenyl polyethoxy ethanol) and 1 ml. of acetone, diluting to200 ml. with water 1,000 ppm. Additional water was used for diluting to200 p.p.m.

The plants were sprayed with the dispersions of the chemicals at thevarious concentrations so that the upper surface of the leaves wasthoroughly wet. The

plants were returned to the greenhouse. The following 1 day (-24 hourslater), rings of an adhesive preparation non-toxic to the organismsunder test, such as is used on fly papers and for ringing trees, wereplaced around the borders of the upper surfaces of the leaves torestrict the mites to the upper leaf surface. Mites were transferred tothe thus treated leaves by placing bean leaflets heavily infested withadult two-spotted spider mites, Tetranychus urticae koch. within theborder of the adhesive preparation on the leaves of the plants undertest. A count of the number of mites transferred was made the same day.The counts ranged from 30 to 300 mites on the six leaves. The plantswere kept in the greenhouse for another 4 days. A final count of thenumber of living mites remaining on the leaves was then made. Thepercent control is found by using the formula:

Percent control 100 (l-(Final count living mites Original count)) 3 Thecontrol of mites by the chemicals of the present invention at thevarious concentrations is shown in the following table (the checktreatments without the chemicals had negligible mortality).

Percent control at Having thus described our invention what we claim anddesire to protect by Letters Patent is:

1. A miticidal composition comprising a miticidally effective amount ofa compound represented by the formula an alkyl group having in which Ris alkyl containing up to 18 carbon atoms, phenyl, phenyl havingsubstituents consisting of up to 5 halo radicals selected from the groupconsisting of chloro and bromo, or mono-substituted phenyl wherein thesubstituent is an alkyl group having up to 9 carbon atoms; R is phenyl,phenyl having substituents consisting of up to 5 halo radicals selectedfrom the group consisting of chloro and bromo, or mono-substitutedphenyl wherein'thesubstituent is an alkyl group having up to 9 carbonatoms; and R is alkyl or haloalkyl having up to 18 carbon atoms,alkenyl, alkynyl having from 3 to 10 carbon atoms, cyclohexyl, phenyl,phenyl havingsubstituents consisting of up to 5 halo radicals selectedfrom the group consisting of chloro and bromo, or mono-substitutedphenyl wherein the substituent is an alkyl group having up to 9 carbonatoms; and a surface-active dispersing agent.

2. A method of controlling mites which comprises applying to plants amiticidally effective amount of a compound represented by the formula r)o ROCIICII:OSORY 0r ROCI'IgCH-O- OR in which R is alkyl containing up to18 carbon atoms, phenyl, phenyl having substituents consisting of up to5 halo radicals selected from the group consisting of chloro and bromo,or mono-substituted phenyl wherein the substituent is an alkyl grouphaving up to 9 carbon atoms; R is phenyl, phenyl having substituentsconsisting of up to 5 halo radicals selected from the group consistingof chloro and bromo, or mono-substituted phenyl wherein the substituentis an alkyl group having up to 9 carbon atoms; and R" is alkyl orhaloalkyl having up to 18 carbon atoms, alkenyl, alkynyl having from 3to 10 carbon atoms, cycl'ohexyl, phenyl, phenyl having substituentsconsisting of up to 5 halo radicals selected from the groupconsisting ofchloro and bromo, or mono-substituted phenyl wherein'the substituent isup to 9 carbon atoms.

2. A method of controlling mites which comprises applying to plants amiticidally effective amount of a compound represented by the formula